Disazo-dyestuffs insoluble in water and fiber dyed therewith



Patented Jan. 26, 1937 2,069,158

DISAZO-DYESTUFFS INSOLUBLE IN WATER AND FIBER. DYED THEREWITH KarlSchnitzspahn, Ofienbach-on-the-Main, and Paul Jfirg,Frankfort-on-the-Main-Hochst, Germany, assignors to General AnilineWorks, Inc., New York, N. Y., a corporation of Delaware No Drawing.Application May 2, 1936, Serial No. 77,638. In Germany May 10, 1935 8Claims. (Cl. 260-84) The present invention relates to disazo-dye- Thefollowing examples serve to illustrate the stuffs insoluble in water andto fiber dyed thereinvention, but they are not intended to limit itwith; more particularly, it relates to compounds thereto; of thefollowing general formula: For producing the dyeings 50 grams of cottonC1 yarn are grounded in the grounding liquor for l I half-an-hour,squeezed and developed for half- N: N=N an-hour in the diazo-solutiomThe material is then rinsed, soaped at boiling temperature, rinsed alkyl01 and dried. 1. (a) Grounding liquor 5 grams of2,3-hydroxynaphthoylaminobenzene are dissolved in a mixture of 10 cc. ofalcohol, 2.5 cc. of formaldehyde of per cent. strength, 2.5

cc. of caustic soda solution of 34 B. and 10 cc. of water and thesolution is added to 1 liter of Water of 35 C., in which 10 cc. ofTurkey red oil insoluble in water are obtainable by diazotizing of50.per cent; strength and 12 of caustic soda an amino-azo-compound ofthe following forsolutlon of 34 have been dlssolved' mula: (b)Diazo-solution alkyl 3.7 grams of the amino-compound of the fol-ONQNQQQNHZ lowing constitution:

' o1 OOH; or O-alkyl I 25 and combining it with an arylide of2,3-hydroxy- N0.Q-N= NH,

naphthoio acid. The amino-azo-compounds may be obtained by couplingdiazotized 1-amino-2,6- 01 C1120 dichloro-4-nitro-benzene withamino-hydroquiare made into a paste with 5 cc. of formic. acid 3none-dialkyl ethers. The new dyestuffs, when of 90 per cent. strengthand stirred together with produced in substance, are valuable blue-blackto 3.2 cc. of sulfuric acid of 36 B. A solution of black pigments. Theyare also especially suit- 0.8 gram of sodium nitrite is run into thismixable for the manufacture of water-insoluble dyeture while cooling.with ice. After about 20 stufis on the fiber, by the ice-color method orby minutes the diazotization is finished. The bath is one of the knownprinting processes, for instance, made up to 1 liter and neutralizedwith 4 grams 0 by the direct printing method. of crystallized sodiumacetate. Blue-black tints The blue-black to black dyestuffs thusobtained of good fastness to light are obtained. are distinguished bytheir good properties of The dyestuff has the following formula:

01 OCH:

15 wherein R stands for a radical of the benzene or naphthalene series.

We have found that valuable disazo-dyestufis of pigments and ice-colors.

o1 orno on fastness. They surpass with respect to fastness 2. (a)Grounding liquor to light the known black dyestuffs obtainable fromdiazotized amino-azo compounds' and arygrams on 3 gt g g lides of2,3-hydroxynaphthoic acid, for instance, naphthalene are dlsso ve m m ga0 by the processes of German Patents'Nos. 293,375, alcohol offormalflehyde cent;

strength, 0.7 cc. of caustic soda so1ut1on of 34 383,903, 391,091 and392,077. They, therefore, 7 represent a valuable enrichment of th massesBe. and 3 cc. of water and the whole is then added to 1 liter of waterof 35 C. containing 10 cc. of

Turkey red oil of per cent. strength and 12 cc. of caustic soda.solution of 34 B.

(b) Diced-solution:

4 grams of the amino-azo-compound of the following constitution:

N O N=N NH:

Cl CaHi) are made into a paste with 5 cc. of formic acid of 90 per cent.strength and stirred together with 3.2 cc. of sulfuric acid of 36 B. Asolution of 0.8 gram of sodium nitrite is run into this mixture whilecooling with ice. After about 20 minutes the bath is made up to 1 literand neutralized with 4 grams of crystallized sodium acetate.

Blue-black dyeings obtained. q i

3. Diazo printz'ngcolor 80 grams of dry diazo-salt containing 20 percent. by weight of the baseof the following formula:

' 01 com N=NQNm o1 c1190 in the form of the, zinc chloride double saltof the diazonium chloride, are stirred with water with addition of 90cc. of acetic acid. of 50 per cent. strength, and 400 grams of wheatstarchtragacanth thickening are added. The whole is made up to 1 kilo. Y

Grounding liquor 15 grams of 1-(2',3' hydroxynaphthoylamino)Z-methyl-benzene, 20 grams of Monopol brilliant oil, 18 cc. of causticsoda solution of 38 B. are dissolved with water and made up to 1 literin the usual manner. 4

Printing prescription The dye goods are padded with the groundingliquor, dried, printed with the diazo-printing color, dried again andthen treated with hot, dilute sodium carbonate solution. The material isthen rinsed, soaped' at boiling'temperature, rinsed again and dried.

Blue-black prints of good fastness to light are obtained.

4. 37.1 grams of the amino-azo-body of the formula: V

01 com OzN N=N NH:

Cl CH3 are diazotized in the usual manner with dilute sulfuric acid andsodium nitrite- The clear (iiazo-solution which has been filtered withsuction is run intoa solution, rendered alkaline with caustic soda, of29.3 grams of 1-(2',3'-hydr0xynaphthoylamino) -2-methoxybenzene, andwhich contains such a quantity of caustic soda solution as is necessaryto maintain a caustic alkaline reof good fastness to light are tained.The following table indicates a number of further azo-dyestufis,obtainable according to the present invention:

Coupling component:

Diazo-component: Tint: 1-(2', 3hydroxynaphthoy1amino) (l)4-amino-2,5-dimethoxy- 3-chloro-4, fi-dimethoxy- Black-blue 2', 6dichloro 4 benzene. nitroazobenzene. (2) Do 2-methyl-4-methoxyben-Black-blue zone. (3) 2, 5-dimethoxybenzene Blue-black (4)4-methoxybenzene Blue-black (5) Z-methyl-i-chloroben- Blue-black zone.(6) Naphthalene Blue-black (7) 3-nitrobenzene Black (8) 4-chlorobenzene.Blue-black (9) 3-chloro-4, fi-dimethoxy- Black-blue benzene. (10)Z-methyl--methoxyben- Black-blue zone. (11) 2, 5-dimethoxybenzeneBlack-blue (l2) Z-methoxybenzene Blue-black 4-methoxybenzene Blue-black(14) z-methyli-chloroben- Blue-black (15) Black-blue (16) Black-blue(17) Blue-black (18) 3-n-itrobenzene Black (19) i-chlorobenzeneBlue-black (20) 2-(2, 3-hydroxynaph- Blue-black thoylann'no)naphthalene.

Since an object of the present invention is to provide dyestufis of goodfastness properties which dyestufis are insoluble in water and alkalies,it is to be understood that the aromatic,

,following general formula:

o0 NH-R wherein R stands for a radical selected from the groupconsisting of the radicals of the benzene and naphthalene series, beingblue-black to black powders and yielding, when produced on the fiber,blue-black to black dyeings of good fastness properties, particularly ofvery good fastness to light.

2. The water-insoluble disazo-dyestuif of the following formula:

01 OCH:

being a blue-black powder and yielding, when produced on the fiber,blue-black dyeings of good fastness properties, particularly of verygood fastness to light.

3. The water-insoluble disazo-dyestufi of the following formula:

OCHs

being a blue-black powder and yielding, when produced on the fiber,blue-black dyeings of good fastness properties, particularly of verygood fastness to light.

5. Fiber dyed with the water-insoluble disazodyestufis as claimed inclaim 1.

OCH:

C1 CH2 01 O C H:

6. Fiber dyed with the water-insoluble disazodyestuff as claimed inclaim 2.

7. Fiber dyed with the water-insoluble disazodyestufi as claimed inclaim 3.

8. Fiber dyed with the water-insoluble disazodyestufi as claimed inclaim 4.

KARL SpI-INITZSPAHN. PAUL JORG.

